Inorganic Battery Materials

Hailiang Wang, Boniface P. T. Fokwa, Hailiang Wang, Boniface P. T. Fokwa

• Publisher: Wiley
• Year: 2019
• Print ISBN: 9781119431992
• eBook ISBN: 9781119432012
• Edition: 1
• Topic: Physical Sciences
• Subtopic: Inorganic Chemistry

A guide to the fundamental chemistry and recent advances of battery materials

In one comprehensive volume, Inorganic Battery Materials explores the basic chemistry principles, recent advances, and the challenges and opportunities of the current and emerging technologies of battery materials. With contributions from an international panel of experts, this authoritative resource contains information on the fundamental features of battery materials, discussions on material synthesis, structural characterizations and electrochemical reactions.

The book explores a wide range of topics including the state-of-the-art lithium ion battery chemistry to more energy-aggressive chemistries involving lithium metal. The authors also include a review of sulfur and oxygen, aqueous battery chemistry, redox flow battery chemistry, solid state battery chemistry and environmentally beneficial carbon dioxide battery chemistry. In the context of renewable energy utilization and transportation electrification, battery technologies have been under more extensive and intensive development than ever. This important book:

• Provides an understanding of the chemistry of a battery technology
• Explores battery technology's potential as well as the obstacles that hamper the potential from being realized
• Highlights new applications and points out the potential growth areas that can serve as inspirations for future research
• Includes an understanding of the chemistry of battery materials and how they store and convert energy

Written for students and academics in the fields of energy materials, electrochemistry, solid state chemistry, inorganic materials chemistry and materials science, Inorganic Battery Materials focuses on the inorganic chemistry of battery materials associated with both current and future battery technologies to provide a unique reference in the field.

About EIBC Books

The Encyclopedia of Inorganic and Bioinorganic Chemistry (EIBC) was created as an online reference in 2012 by merging the Encyclopedia of Inorganic Chemistry and the Handbook of Metalloproteins. The resulting combination proves to be the defining reference work in the field of inorganic and bioinorganic chemistry, and a lot of chemistry libraries around the world have access to the online version. Many readers, however, prefer to have more concise thematic volumes in print, targeted to their specific area of interest. This feedback from EIBC readers has encouraged the Editors to plan a series of EIBC Books [formerly called EIC Books], focusing on topics of current interest.

EIBC Books will appear on a regular basis, will be edited by the EIBC Editors and specialist Guest Editors, and will feature articles from leading scholars in their fields. EIBC Books aim to provide both the starting research student and the confirmed research worker with a critical distillation of the leading concepts in inorganic and bioinorganic chemistry, and provide a structured entry into the fields covered.

Part 1
Chemistry of Li‐Ion Battery Materials

Silicon‐Based Anodes for Advanced Lithium‐Ion Batteries

Junhua Song, Xiaolin Li and Ji‐Guang Zhang

Pacific Northwest National Laboratory, Richland, WA, USA

1. 1 Introduction
2. 2 Nanostructure Design
3. 3 Binder Effect
4. 4 Electrolyte Optimization and Interphase Engineering
5. 5 Practical Perspectives of S‐Based Anodes in Full Cells
6. 6 Challenges and Outlook
7. 7 Abbreviations and Acronyms
8. 8 References

1 Introduction

Since the commercial introduction of lithium‐ion batteries (LIBs) in 1990s by Sony Corporation, the quest for high energy density rechargeable batteries has become burgeoningly active.(1–3) In the past decades, the energy density has taken a threefold increment from the first‐generation LIB (80 Wh kg⁻¹) to today's 240 Wh kg⁻¹.(4) The advancement of battery performance has been driven by several technical breakthroughs, such as the discovery of layered transition‐metal oxide cathode material, LiCoO₂, in the 1980s by John Goodenough,(5,6) and using carbonaceous anode materials as Li‐ion hosts. With the continuous efforts on the optimization of materials processing, improvements on the inactive components (including electrolyte, separator and binder, conductive additive, and current collector) and engineering progress in manufacturing, the ceiling of Li‐ion's energy density is approaching its theoretical limits with the general concept of insertion anode and cathode pair. While technological achievements play a key role in boosting the LIBs' performance, the consumer demands, growing consciousness of sustainability, and pursue of cost‐effectiveness in production have also driven the research for further improvements of the already powerful Li‐ion chemistry. Nowadays, the surging number of the electrical vehicles (EVs) is gradually taking the dominating role in consuming high energy density LIBs, while their demands were marginally low in 2010 compared to those used in computers, consumer electronics, and cameras, also known as the 3C market.(7,8) However, the growing trend of electrifying the transportation systems requires a leap in the LIB technology to significantly extend the driving distance of EVs so that consumers can be freed from the range anxiety. Similar to the technical breakthroughs before the birth of Li‐ion chemistry, finding a high‐performance anode material holds a great promise meeting the increasing demand on LIBs' energy density, reliability, and low cost. The state‐of‐the‐art graphite anode has been the top choice in today's LIBs with its low charge/discharge potential, moderate capacity of 372 mAh g⁻¹, and low manufacturing cost (Table 1). Among all the alternative anode materials, silicon (Si) is considered the most promising candidate for the next‐generation high‐energy LIBs for several reasons: (i) Si has a theoretical specific capacity of 4200 mAh g⁻¹ and volumetric capacity of 9786 mAh cm⁻³ upon full lithiation (Li_4.4Si), which are ∼10 times larger than graphite(9); (ii) the lithiation/delithiation potential averages at ∼0.4 V versus Li, which ensures a relatively high operation voltage in full cell configuration as well as prevents safety concerns caused by lithium plating at low anode voltage(10); (iii) the potentially low toxicity, low cost, environmental friendliness, and natural abundance of Si render it the most suitable substitution to graphite anode. Nevertheless, the promises never come without a challenge. The efforts to make Si anodes practically adopted in LIBs have gone through a long research development process that is not completed yet.

Tab. 1 Comparison of the state‐of‐the‐art anode materials for LIBs

Anode	Graphite	Silicon	LTO	Lithium
Gravimetric capacity (mAh g^−1)	372	4200	175	3862
Volumetric capacity (mAh cm^−3)	837	9786	613	2047
Volume change (%)	12	420	1	∞
Average potential vs Li (V)	0.05	0.4	1.6	0
Cost	Low	Low	Medium	High

Early trials in the 1970s using Li–Si alloy in electrochemical cells operated at elevated temperature >400 °C and suffered poor reversibility at room temperature owing to the large volume change.(11,12) Since then, tackling the structural damage and improving its room temperature performance have been the research focus of using Si‐based anode in LIBs. In the early 1990s, Dahn et al. examined the Si_xO_yC_z glass composite derived from Si‐containing polymers. By tuning the Si content in the final product, his group was able to achieve a reversible capacity of 900 mAh g⁻¹ at room temperature in half‐cell configuration.(13) Their results marked the possibility of replacing graphite with high‐capacity Si as anode in LIBs. As materials science research entered the nano era, it also encouraged the exploration of using nano‐sized Si as anode materials in the late 1990s. To fabricate nanoscale Si with controllable size, Si film was made with chemical vapor deposition (CVD) and able to achieve a capacity as high as 1000 mAh g⁻¹, despite the cyclability being quite limited due to the structural breakdown associated with huge volume change of the thin‐film electrode.(14) Later at the beginning of the twenty‐first century, several major material breakthroughs have taken place in the Si anode research. One is to construct composite Si alloys (FeSi₂, NiSi₂, and BaSi₂), which effectively extends...

Table of contents

• Cover
• Table of Contents
• Encyclopedia of Inorganic and Bioinorganic Chemistry
• Editor‐in‐Chief Emeritus & Senior Advisors
• Contributors
• Series Preface
• Volume Preface
• Part 1: Chemistry of Li‐Ion Battery Materials
• Part 2: Lithium Metal Battery Materials
• Part 3: Materials and Chemistry of Non-Lithium Batteries
• Part 4: Electrolyte Chemistry for Rechargeable Batteries
• Part 5: Advanced Characterizations of Inorganic Battery Materials
• Index
• Abbreviations and Acronyms used in this Volume
• End User License Agreement